Disazo dyestuffs containing a bridging group and at least one quaternary ammonium group

ABSTRACT

DISAZO COMPOUNDS OF THE FORMULA   D-N=N-A-N(-R&#39;&#39;)-R&#34;   D-N=N-(A-N-(-R&#39;&#39;)-R&#34;)-Z-(N(-R&#39;&#39;)(-R&#34;)-A)-N=N-D   IN WHICH D REPRESENTS THE RESIDUE OF A MONOCYCLIC OR BICYCLIC DIAZO COMPONENT, A REPRESENTS AN ARYLENE RESIDUE AND R&#39;&#39; AND R&#34; EACH REPRESENTS AN ALKYL RESIDUE, ARE LINKED TOGETHER VIA THEIR COUPLING COMPONENTS THROUGH A BIFUNCTIONAL BRIDGING GROUP Z WHICH HAS NO DYESTUFF CHARACTERTISTICS AND WHICH CONTAINS AT LEAST ONE QUATERNATED NITROGEN ATOM. THE COMPOUNDS ARE USEFUL FOR DYEING AND PRINTING SYNTHETIC FIBERS, AND PRODUCE INTENSE AND LEVEL DYEINGS POSSESSING GOOD FASTNESS TO LIGHT, WASHING, PERSPIRATION AND SUBLIMATION.

United States Patent 3,635,940 DISAZO DYESTUFFS CONTAINING A BRIDGINGGROUP AND AT LEAST ONE QUATERNARY AMMONIUM GROUP Gert Hegar,Schoenenbuch, Hans-Joerg Angliker, Riehen, and Richard Peter, Basel,Switzerland, assignors to Ciba Limited, Basel, Switzerland No Drawing.Filed May 21, 1968, Ser. No. 730,943 Claims priority, applicationSwitzerland, May 29, 1967, 7,532/67 Int. Cl. C09b 33/06, 43/00; D06p1/02 U.S. Cl. 260-455 9 Claims ABSTRACT OF THE DISCLOSURE Disazocompounds of the formula DN=NA-N/ in which D represents the residue of amonocyclic or bicyclic diazo component, A represents an arylene residueand R and R" each represents an alkyl residue, are linked together viatheir coupling components through a bifunctional bridging group Z whichhas no dyestutf characteristics and which contains at least onequaternated nitrogen atom. The compounds are useful for dyeing andprinting synthetic fibers, and produce intense and level dyeingspossessing good fastness to light, washing, perspiration andsublimation.

The present invention provides new and valuable disazo compounds inwhich two monoazo dyestuff molecules of the general formula RIDN=N'A--N/ RII in which D represents the residue of a monocyclic orbicyclic diazo component, A represents an arylene residue and R and Reach represents an alkyl residue, are linked together via their couplingcomponents through a bifunctional bridging group Z which has no dyestuffcharacteristics and which contains at least one quaternated nitrogenatom. Generally, the symbol A stands for a 1,4-phenylene residue.

Accordingly, the invention provides, for example, disazo compounds ofthe formula in which x x x and x each represents zero or 1 and 1+ 2+ a+4= 1, 2, la 'z 'a and 4 each represents a hydrogen atom or preferably analkyl group that may be substituted and in which when x =1 and/ or 96:1, R may be bound to the residue A to form a ring and/or R may be boundto the residue A to form a ring; R and R each represents an alkylenegroup that 3,635,940 Patented Jan. 18, 1972 may be substituted; A and Aeach represents a phenylene residue that may be substituted and in whichthe azo group and the secondary or tertiary amino group are in1,4position to each other; D and D each represents the residue of amonocyclic or bicyclic diazo component, the residue of a diazo componentof the benzene or naphthalene series, and Z represents a bifunctionalbridging group which has no dyestuif characteristics and which containsat least one quaternated nitrogen atom.

The invention may be further defined as follows: a disazo compound asshown in the formula in column 1, in which x x x and x each representszero or 1 and x +x +x +x =2; R R R R' R;, and R, each represents alkylof up to 4 carbon atoms, cyanoalkyl of up to 3 carbon atoms, alkoxyalkylof up to 5 carbon atoms, hydroxyethyl, nitroethyl, chloroethyl,B,B,B-trifiuoromethyl, alkanoylaminoalkyl of up to 4' carbon atoms,alkanoyloxyal'kyl of up to 5 carbon atoms, alkylsulfonylalkyl of up to 4carbon atoms, ,B-(p-cholorbenzenesulfonyl)-ethyl, Bmethylcarbamyloxyethyl, ,6 phenylcarbamyloxyethyl,B-phenylcarbamyloxyethyl, alkyl-oxycarbonyloxyalkyl of up to 6 carbonatoms, v acetamidopropyl, ,8 (para-nitrophenoxy)-ethyl,p-(para-hydroxyphenoxy)-ethyl, (3-(fl-acetylethoxycarbonyl)-ethyl,B-[fi'- (cyano -ethoxycarbonyl] -ethyl, l3- /3'- (hydroxy-ethoxycarbonyl] -ethyl, 18- [i'- (methoxy -ethoxycarbonyl] -ethyl, Sf-[3 (acetoxy)-ethoxycarbonyl]-ethyl, ,B-carboxyethyl, 3 aminopropyl,fi-diethylamino-ethyl, B-cyanoacetoxyethyl, fatty acid acyloxyalkylcontaining up to 5 carbon atoms, or C -C phenylalkyl, and when said R isbound to A forms a tetrahydro-quinoline ring and when said R is bound toA forms a tetrahydro-quinoline ring; R and R each is alkylene of up to 3carbon atoms or a group of the formula wherein Ac represents alkanoyl ofup to 3 carbon atoms, benzoyl, stearoyl, methanesulphonyl,ethanesulphonyl, para-toluenesulphonyl, phenoxycarbonyl,methoxycarbonyl, phenylaminocarbonyl, methylaminocarbonyl oraminocarbonyl residue; A and A each is a phenylene group of the formulawherein C and d each represents hydrogen, C -alkyl, C -alkoxy,acetylamino, phenoxycarbonylamino, methoxycarbonylamino oraminocarbonylamino; the azo group and the dialkylamino group in saidformula are attached in para-position to each other; D and D eachrepresents the residue of a diazo component of the benzene ornaphthalene series and Z is selected from the group consisting of (l) aresidue of the formula --NH-COZ-CO-NH-- wherein Z is a heterocycliccontaining up to 6 carbon atoms and containing hetero atoms selectedfrom the group consisting of nitrogen and oxygen,

(2) a group selected from the formula and Re Rs in which Y* representsan anion and R and R together form an alkylene chain that may beinterrupted by a hetero atom selected from the group consisting ofnitrogen, oxygen and sulfur and contains up to 5 carbon atoms;

(3) when R, and R form a part of a tetrahydroquinoline structure, orwhen X; or X; is 1, or when R and R are B-acetoxy-propylene, Z is agroup of the formula 5+ 7 R's Re wherein R' and R' are C -C -alkyl; or agroup of the formula and more particularly compounds of said formulawherein x x x and x each represents zero or 1 and i-lz-ls+-"4 R R R R Rand RC; each represents alkyl of up to 4 carbon atoms, cyanoalkyl of upto 3 carbon atoms, alkoxyalkyl of up to 5 carbon atoms, hydroxyethyl,fatty acid acyloxyalkyl containing up to 5 carbon atoms, or C C-phenylalkyl, and when said R is bound to A forms a tetrahydro-quinolinering and when said R is bound to A forms a tetrahydroquinoline ring; R;and R each is alkylene of up to 3 carbon atoms or alkylene substitutedwith alkylcarbonyloxy containing up to 3 carbon atoms; A and A each isphenylene or phenylene substituted with methyl, methoxy, chlorine oracetylamino; the azo group and the dialkylamino group in said formulaare attached in para-position to each other; D and D each represents theresidue of a monocyclic or bicyclic diazo component of the benzene ornaphthalene series and Z is selected from the group consisting of--NHCOZ'=CONH wherein Z is a heterocyclic containing up to 6 carbonatoms, and containing hetero atoms selected from the group consisting ofnitrogen and oxygen;

(2) a group selected from the formulae Y Y -N C1-C -alkylen;N- R5 R Rand R 5 R in which Y- represents an anion and R and R together form analkylene chain that may be interrupted by a hetero atom selected fromthe group consisting of nitrogen, oxygen and sulfur, and contains up to5 carbon atoms,

(3) when R and R form a part of a tetrahydroquinoline structure, or whenX or X, is 1, or when R and R are fl-acetoxy-propylene, Z is a group ofthe formula in which Y- represents an anion and R and R each representsan alkyl, aralkyl or cycloalkyl group, and in which R and R together mayform an alkylene chain that may be interrupted by a hetero atom or partof an aromatic ring.

The dyestufis of the invention are generally free from carboxylic andsulphonic acid groups. The diazo residues D and D may be identical ordifferent and are principally derivatives of monocyclic or bicyclicamines or any diazotizable heterocyclic amine which is free from acidicsubstituents imparting solubility in water, but especially aminescontaining a five-membered heterocyclic ring having two or three heteroatoms, especially one nitrogen atom and one or two sulphur, oxygen ornitrogen atoms, and aminobenzenes, especially those of the formula inwhich :1 represents a hydrogen or a halogen atom or an alkyl, alkoxy,nitro, cyano, carbalkoxy or alkylsulphone group, b represents a hydrogenor a halogen atom or an alkyl, cy-ano or trifluoromethyl group and 0'represents a nitro, cyano, carbalkoxy or alkylsulphonyl group.

The following are given as examples:

Z-aminothiazole, 2-amino-5-nitrothiazole,2-amino-5-methylsulphonylthiazole, Z-amino-S-cyanothiazole,Z-amino-4-phenylthiazole, 2-amino-4-methyl-S-nitrothiazole,2-amin0-4-methylthiazole, 2-amino-4- 4-chloro -phenylthiazole,2-amino-4-(4-nitro)-phenylthiazole, S-aminopyridine, 3-aminoquinoline,3-aminopyrazole, 3-amino-l-phenylpyrazole, S-aminoindazole,3-amino-1,2,4-thiazole, 3-amino-5-(methyl-, ethyl-, phenylorbenzoyl)-l,2,4-

triazole, 3-amino-l-(4-methoxyphenyl)-pyrazole, 2-aminobenzthiazole,2-amino-6-methylbenzthiazole, Z-amino-6-methoxybenzthiazole,2-amino-6-chlorobenzthiazole, 2-amino-6-cyanobenzthiazole,2-amino-6-thiocyanobenzthiazole, Z-amino-6-nitrobenzthiazole,Z-amino-6-carboethoxybenzthiazole, 2-amino-4(4- or6-)methylsulphonylbenzthiazole, Z-amino-1,3,4-thiadiazole,2-amino-1,3,5-thiadiazole, 2-amino-4-phenylor-4-methyl-l,3,S-thiadiazole, Z-amino-S-phenylor-5-methyl-1,3,4-thiadiazole, 2-amino-3-nitro-5-methylsulphonylthiophene,2-amino-3,5-bis-(methylsulphonyl)-thiophene,5-amino-3-methyl-isothiazole, 3- or 4-aminophthalimide, aniline,1-amino-3- or -4-chlorobenzene, 1-amino-4-bromobenzene, 1-amino-2-, -3-or -4-methylbenzene, 1-amino-2-, -3- or -4-nitrobenzene,1-amino-4-cyanobenzene, l-arninobenzene-3- or -4-methylsulphone,1-amino-2-chlor0benzene-4-methylsulphone, l-amino-2,S-dicyano-benzene,1-amino-4-carbethoxybenzene, 1-amino-2,4- or -2,5-dichlorobenzene,1-amino-2,4-dibromobenzene, 1-amino-2-methyl-4- or -6-chlorobenzene,l-amino-2-trifluoromethyl-4-chlorobenzene,1-amino-2-cyano-4-chlorobenzene, l-amino-2-cyano-nitrobenzene,1-amino-2-carbometh0xy-4-chlorobenzene,1-amino-2-methanesulphonyl-4-chlorobenzene,1-amino-2-carbomethoxy-4-nitrobenzene,

1amino-2-phenoxy-4-nitrobenzene, 1amino-2-chloro-4-cyanobenzene,1-amino-2-chloro4-nitrobenzene, l-amino-Z-rnethoxy-4-nitrobenzene,l-amino2-chloro-4-carbethoxybenzene, 1-amino-2,4-dinitrobenzene,1-amino-2,4-dicyanobenzene, l-arnino-Z,6-dichloro-4-cyanobenzene,l-amino-2,6dichloro-4-nitrobenzene, 1-amino-2,5- or2,6-dichlorobenzene-4-sulphonic acid dimethylamide,1:amino2-chlorobenzene-4-sulphonic acid dimethylamide,1amino-Z,6-dibromobenzene-4-sulphonic acid amide,l-amino-Z,4-dinitro-6-ch1oroor 6-bromobenzene,1amino-2,4-dicyano-6-chlorobenzene, l-amino-2,4,6-trichloroortribromobenzene, 1-aminobenzene-3- or 4-sulphonic acid amide,1-aminobenzene-3- or 4-sulphonic acid-N-methylor diethylamide,4-aminoazobenzene, 4-amino-2'-chloroazobenzene,4-amino-2',4-dichloroazobenzene, 4-amino-3'-chloroazobenzene,4-amino-2-nitroazobenzene, 1amino-4-nitrobenzene-Z-methylsulphone,1aminobenzene-4-carboxylic acid-fl-methoxyethylester,4-amino-3nitroazobenzene, 4-amino-3'-nitroazobenzene,4-amino-2methylazobenzene, 4-amino-4-methoxyazobenzene,

, 4-amino-3nitro-2-chloroazobenzene,

4-amino-3-nitro-4'-chloroazobenzene,4-amino-3nitro-2,4'-dichloroazobenzene,4-amino-3nitro-4'-methoxyazobenzene, 4-aminodiphenyl and 2- or4-aminodiphenylether.

The groups A and A are preferably residues of the formulae Q d1 dz inwhich c d, and d each represents a hydrogen atom or a methyl, ethyl,methoxy, ethoxy, phenylthio or phenoxy residue.

The groups c and c are preferably bound in orthoposition to the azogroup and, in addition to the abovementioned groups, may also representa chlorine or a bromine atom, a trifiuoromethyl group, an alkylsulphonylgroup, preferably a methylsulphonyl group and an acylamino group thatmay be alkylated, preferably methylated, at the nitrogen atom and inwhich the acyl residue is the residue of an organic monocarboxylic acid,an organic monosulphonic acid, for example, methane-, ethaneorpara-toluene-monosulphonic acid, or the residue of a carbamic acid or acarbonic acid monoester or monoamide, for example, phenoxycarbonyl,methoxycarbonyl and aminocarbonyl.

The pairs of substituents R and R R' and R and R' and R, preferably havethe same meaning. They may be hydrogen atoms or low alkyl groups, thatis to say, alkyl groups containing 1 to 4, preferably 2 to 4, carbonatoms, for example, methyl, ethyl, n-propyl or n-butyl groups, that maybe substituted in the usual manner, for example, benzyl or B-phenylethylgroups, halogenated alkyl groups, for example, fl-chloroethyl,3,B,B-trifluoroethyl and ,Bgy-dichloropropyl-B-cyanoethyl groups,alkoxyalkyl groups, for example, B-ethoxyethyl or 'y-methoxybutylgroups, hydroalkyl groups, for example, fl-hydroxyethyl and;3,'y-dihydroxypropyl groups, nitroalkyl groups, for example,,s-nitroethyl groups, carbalkoxy groups, for example, B-carbo-(methoxy-,ethoxyor propoxy)-ethyl groups (in which the terminal alkyl group maycarry cyano, carbalkoxy, acyloxy and amino groups in w-position) and ,8-or 'y-carbo-(methoxyor ethoxy)-propyl groups, acylaminoalkyl groups, forexample, B-(acetylor formyl)-aminoethyl groups, acyloxyalkyl groups, forexample, B-acetyloxyethyl and 5,'y-diacetoxy propyl groups, ,B-(alkyloraryl)-sulphonylalkyl groups, for example, fl-methanesulphonyL, ethyl-,[i-ethanesulphonylethyl or ,8-(para-chlorobenzenesulphonyl)ethyl groups,alkylor arylcarbarnoyloxyalkyl groups, for example, ,8-methylcarbamyloxyethyl and fl-phenylcarbamyloxyethyl groups,alkyloxycarbonyloxyalkyl groups, for example, 5- (methoxy-, ethoxyorisopropyloxy)carbonyloxyethyl, acetamidopropyl,3-(para-nitrophenoxy)ethyl, B-(parahydroxyphenoxy)-ethyl, 6 (13'acetylethoxycarbonyl)- ethyl, B-[pV-(cyand, hydroxy-, methoxy oracetoxy)- ethoxycarbonylfl-ethyl, cyanoalkoxyalkyl, B-carboxyethyl,fl-acetylethyl, S-aminopropyl, B-diethylaminoethyl, fi-cyanoacetoxyethyland fl-benzoyl-fl-(para-alkoxyor phenoxy-benzoyl)-oxyethyl groups. Ingeneral, these groups contain not more than nine carbon atoms.

The alkyl residues R and R are, for example, 1,2- alkylene or1,3-propylene groups or bridging groups of the formula which may beacylated. The acyl residue Ac is the residue of an organicmonocarboxylic acid, a monosulphonic acid, a carbamic acid or a carbonicacid monoester or monoamide, for example, an acetyl, formyl, propionyl,benzoyl, stearoyl, methanesulphonyl, ethanesulphonyl,para-toluenesulphonyl, phenoxycarbonyl, methoxycarbonyl,phenylaminocarbonyl, methylaminocarbonyl or aminocarbonyl residue.

When the groups R or R are bound to a group A or A in ortho-position toform a ring, tetrahydroquinoline or benzomorpholine residues, forexample, are present, and the groups of the formulae A1NR1R3-- and/orA2-NR2R4- are then derived, for example fromN-B-hydroxyethyl-l,2,3,4-tetrahydroquinoline,

N-fl-v-dihydroxypropyl-1,2,3,4-tetrahydroquinoline,

N-Bn-dihydroxypropy1-7-methoxy-1,2,3,4-tetrahydroquinoline,

N1 ,'v-dihydroxypropyl-S-acetylamino-1 ,2,3 ,4-tetrahydroquinoline,

N-fl-hydroxyethyl-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline,

N-jS-hydroxyethylbenzomorpholine and N-fl-dihydroxypropyl-S-acetylaminobenzomorpholine.

The groups R and R are alkyl, aralkyl or cycloalkyl groups, for examplemethyl, ethyl, propyl, benzyl or cyclohexyl groups or, together with thenitrogen atom that binds them, they form a pyrrolidine, piperidine,a,,8-'ymethylpiperidine, morpholine, thiomorpholine ortetrahydroisoquinoline ring.

The residue Y is the anion of a strong organic or inorganic acid, forexample, Cl, Br, I, =SO SO -alkyl, --SO -,-aryl or S0 O-alkyl.

The bifunctional bridging group Z is principally a group correspondingto one of the following formulae in which R, is the residue of adicarboxylic acid freed from the carboxyl groups;

in which R is the residue of a diisocyanate freed from the isocyanategroups, and

it 1 -IIICHzCH CHg-NH-SOg-Rn-SO -NH-CHzcHzoHr-lrl Re I ia in which R isthe residue of a disulphonic acid freed from the sulphonic acid groups.45

Specially preferred are diazo compounds which contain a monoazo residueof the formula "Y- D,-N=N-A,-NR1-R, 1 i1z m 5 0 in which R and Rtogether may constitute an ethylene bridge when the residue R representsan ethylene bridge, and especially the disazo dyestuffs of the formulaein the symb0ls D1, D2, A1, A2, R1, R2, R3, R4, R R and Y have themeanings ascribed to them in the above formula.

The new dyestuffs may be obtained by (a) coupling 70 two couplingcomponents of the formula which are linked to each other through abifunctional bridging group Z which has no dyestutf characteristics andwhich contains at least one quaternated nitrogen atom, in which FormulaA represents the residue of an arylene component and R' and R" eachrepresents an alkyl group, with diazo compounds derived from amines 0fthe formula D NH and D NH to form disazo compounds, the symbols D and Deach representing monocyclic or bicyclic residues, or (b) reacting twoidentical or different dyestuffs of the formula in which D and R havethe meanings given above, A represents an arylene residue and Rrepresents an alkyl group, and in which a reactive substituent ispresent in one of the residues A and R', either simultaneously orsuccessively in two steps with compounds which yield the bifunctionalbridging group Z which has no dyestuff characteristics, or (c) treatingwith quaternating agents a disazo compound in which two monoazo dyestuifmolecules of the formula RI DN=NAN are linked through a bridging group Zwhich contains at least one nitrogen atom capable of being quaternatedand has no dyestuff characteristics.

(I) PROCESS (a) (A) Coupling components The coupling components for usein process (a) of the invention are preferably those of the formula inwhich x x x and x each represents zero or 1 and x +x +x +x =2; R1, R2, Rl, Rz, R':; and R'4 each repsents a hydrogen atom or preferably an alkylgroup, and in which when x =1 and/or x =1, R may be bound to the residueA to form a ring and/or R may be bound to the residue A to form a ring;R and R each represents an alkylene group; A and A each represents aphenylene residue in which the azo group and the secondary or tertiaryamino group are in 1,4-position to each other and Z is bifunctionalbridging group which has no dyestuif characteristics and which containsat least one quaternated nitrogen atom. They may be coupled with diazocompounds derived from amines of the formulae D NH and D NH in which Dand D have the meanings given above.

The coupling components which may be used in the synthesis of thedyestuffs of the invention are, for example, the compounds correspondingto the following formulae:

9 10 C2H4CN acetic acid dichloride and subsequent quaternation of theimino rou N g int-( 1m g p) c n N+ CH2 R2 H2 H2 5 HA 1-N 1'35 N-A 21102114 CHQOH -Ii -OH CH O?OCH C 2 \N Re 2 (manufactured, for example, byreacting an N-,8-chloroethyl-N-alkylaniline with monoethanolamine,quaternation of the aliphatic nitrogen atom and subsequent reaction witha chloroformic acid ester of an N-fl-hydroxyethyl- N-alkylaniline) Eom-om ri-ong-onz 1 H3 H-A1-N 1'1 N-Az-H I C'7H7SO3 CH OH (f-O-CHCHQ-IIICHZCH -O-fiJ-CHgOHa Ra 0113002114 02114 01 N (manufactured, forexample, by reacting 2 mols of an acid C H chloride or chloroformic acidester of an N-p-carboxy- J 2 4 5 ethyl-N-alkylaniline with adiethanolalkylamine and sub- C2H4 H3 sequent quaternation): CHPCHFCNNCAJEPCEQ CH2CH2 CHgCHg S HA1N N-CHgN N-A -H o11 -o11-oH -N:o112011-orr2 CHHJQ CHZCHZ the doubly quaternated coupling components of thefor- 4Hn CHaSOF mulae r r HA.l--N'CH2CH2CH2 1$ CH2C H2O I2 NI'ICO R1NH CO CH2 C Hg C H2IIIC H2O H2CH2 NA 2-H Ra Ra R1 R5 R5 R2 and in which thegroup Ac represents the residue of an organic monocarboxylic acid:

(manufactured, for example, by acylation of an N-(vaminopropyl)-N-alkylaniline with a 'y-N,Ndimethylaminopropionic acid halide andalkylation of the tertiary amino groups with an N-S-chloroethyl-N-alkylaniline):

(manufactured, for example, by esterification of 2 mols ofN-B-hydroxyalkyl-N-alkylaniline with 1 mol of iminodiwith 1 mol of adicarboxylic acid or disulphonic acid halide or with 1 mole of adiisocyanate and then quaternatmg.

Also suitable or the compounds of the formula C1 C2 in which c 0 d and dhave the meanings given above and X represents an aliphatic,cycloaliphatic or araliphatic residue, for example, the couplingcomponents indicated in the following table:

TABLE 1 I CH -CH;

mmmmmmmme .e

mmmmmmmmm e mmmmmmmmm e 11 12 and the trebly quaternated couplingcomponents of the a nozzle, preferably under pressure. The mixing nozzleformulae may be constructed and operated, for example, on the /R1 R2\H-A1-N 1P5 IP15 1E5 /NAz-HCHgCHHz-IFCH2CHzfi-QCHgCl'Ig-Jfi-ClizCflr-O-fiCHzCHzI-OHzCHzCHg Ru 0 Re0 Ba (manufactured, for example, by reacting 2 mols of the principle ofthe water jet pump, the supply of one of the adduct of acrylic acidethylester and an N-y-arnino-N- liquids to the mixing nozzlecorresponding to the supply alkylaniline with diethanolalkylamine andthen quaterof water in the water jet pump, and the supply of the othernating): liquid corresponding to the connection between the water R1 R2H-Ar-N 5 !1C3H7 1'15 /NA2H CH GHgGH N+-CH GHCH N+OH2(FHCH III+-CHzCHzCHRs OH Ra OH Ru (manufactured, for example, by additively combining 1 jetpump and the vessel to be evacuated; feed of the liquid mol ofN,N-diglycidyl-N-propylamine with 2 mols of N- through the latter supplyroute may also be effected under 'y-aminopropyl- -alkylaniline).pressure.

Finally, mention may also be made of the bifunctional Other devices toeffect rapid and, if necessary, continucoupling components correspondingto the following forous mixture in a small space may also be used.mulae: After coupling, the non-quaternated dyestuffs that are I IHCO LNCO--HN 135 Y- -o0 (Jo-b d formed can easily be separated from thecoupling mixture,

for example, by filtration, because they are virtually in- RQR NQ Y-NR2R'4 soluble in Water. When the dyestuffs obtained are quaterl nated,they may be salted out. When a bifunctional coupling component iscoupled R R with less than two mols of a diazonium compound, a mix- 5ture of the disazo dyestuffs of the invention and monoazo (B) Diazocomponents dyestuffs is formed, and this process is also included in thepresent invention. The diazo components which may be used are, forexample, the amines corresponding with the definition of the Processdiazo residues D and D The new dyestuffs may also be obtained by process(b) c Diazotization and coupling of the invention in which two monoazodyestuffs are linked together. One of the two monoazo dyestuffs mayDiazotization of the above-mentioned diazo components already contain aquaternated amino group, or, prefer may be e e y k1 10W11 P i for P f aably, it may be formed during the linking process. To mlneral acid andsodium nitrite or, for example, with a this end, a monoazo dyestuff ofthe formula solution of nitrosylsulphuric acid in concentrated sulphuricacid. D1 =NA NR Z P QE y also be calried lfllowfl q for in which D A andR have the meanings given above example, In a nfflltfal t0 acld 1fHeCeS$aTy, 1I1 i and the residue Z corresponds, for example, to theforpresence of sodium acetate or a similar buffer which 1nl R3 NR5R6, inwhich R3, R5 and R6 have the flll n s th I P g a Catalyst, for eXamPIe,meanings given above, is reacted with a monoazo dyedimethylformamide,pyridine or the salts thereof. 7 mg f the f l Coupling may also beeffected advantageously by combining components in a mixing nozzle. Bymixing nozzle DTN=N AZ NRF X is meant a device in which the liquids tobe mixed are in which, for example, X represents -R -Y and R andcombined with one another in a comparatively small space, Y have themeanings given above, together with quaternawhereby at least one of theliquids is conducted through tion to form the disazo dyestuif.

13 14 For example, adyestuff of the formula (3) The diazo residues D andD are more easily quaternatable. In this case, when process (c) isadopted, D N N G only those dyestuffs in which D D and Z are quaternatedare obtained.

CH2CH3OSOCH:42 5 In this process the disazo dyestuffs are quaternatedwith esters of strong mineral acids or organic sulphonic acids,

y be reacted with a dyestuff of the formula for example, dimethylsulphate, diethyl sulphate, alkyl halides, for example, methyl chloride,methyl bromide or D methyl iodide, aralkyl halides, for example, benzylchloz ride, esters of loW-molecular-weight alkanesulphonic CHZCHPMCHBMacids, for example, the methyl ester of methane-, ethaneto form adyestuff of the formula or butane-sulphonic acid, and the alkyl estersof (4-metho11 oH -1-i-----omo CH; CH;

The two halves of the dyestuff may be identical or yl-, 4-chloroor 3- or4-nitro)-benzene sulphonic acid different. This reaction is carried outunder the same 0 which, as anions, form halogen, sulphuric acidsemi-ester, conditions as the quaternation described below. alkane orbenzene sulphonic acid anions.

Quaternation is preferably effected by heating in an (In) PROCESS (c)inert organic solvent, for example, xylene, carbon tetra- The new y f yalso be obtalned y treatlng chloride, ortho-dichlorobenzene ornitrobenzene. Alternawith a qnatemanng agent one of the dyesnlfisdesenbed tively, it is possible to use solvents for example aceticabove, in which the Symbol Z represents a bifunenonal anhydride,dimethylformamide, acetonitrile or dimethyl bridging group containingleast one quatefnata'hle sulphoxide. The quaternatable dyestuffspreferably controgen atonl- It is Specially advantageous to qnaterna'letain as anion Y- the residue of a strong acid, for example the dyestuffsof the formulae sulphuric acid or a semiester thereof, or a halogen ion,but they may also be used as double salts, for example, with 21110chloride, or as free bases.

CHZCHQ1TICH2C 2 (IV) USE 5 v In so far as they are 1n the form of saltsof strong in- R1 organic acids which form more or less neutral aqueoussolutions, the azo dyestuffs used in accordance. with the invention maybe applied in a slightly alkaline, neutral or I OHZCH CHT N OHFCH CH2slightly acid bath. It is advantageous to carry out dyeing A0 0A0 in anacidic bath to which the acid required, for example, in which thesymbols R R R A A D D and Ac acetic acid, formic acid, tartaric acid, anaphthalene sulhave the meanings given above. phonic acid, an alkalibisulphate, sulphuric acid, an acidic The dyestuffs of the followingformulae may be menalkali metal phosphate or phosphoric acid is added attioned as starting materials for the quaternation: the commencement ofthe dyeing process, or to which OOOOH: OCOCHa and a substance is addedwhich liberates acid during the dyeing process. Substances which produceacid are, for Dr-N=N- -NR1'R,' R,'R4'N N=N=D, example, salts of volatilebases and strong, non-volatile acids, for example, ammonium sulphate, orwater-soluble esters of organic acids, which are saponified during thedyeing process, for example, the methyl or ethyl esters NHOO COHN ofaliphatic hydroxy-acids, for example, lactic, malic or N tartaric acid.When mineral acid solutions of the dyestuffs Given that 1= 2, thefollowing three Sets of eondi' to be used in accordance with theinvention are employed, tions may obtain, depending on thequaternatability of th i l id may als b b ffe d durin h dyeing the diazoresidues D and D and the quaternatable niprocess by the gradual additionof alkali metal salts of trogen atoms present in the quaternatableresidue: weaker acids, for example, sodium acetate. Dyeing may The diazoresidues D and 2 are not q rn be carried out in an open vessel at theboil or in a closed a This pplies, for ex pl in th Case of negativelyvessel under superatmospheric pressure at a temperature substitutedanilines, when dyestuffs are obtained which above 100 C. The azodyestuifs in accordance with the can be. quaternated only in thebridging group Z. invention may be used for dyeing and printing a verywide (2) The diazo residues D and D are more difficult variety ofsynthetic fibres, for example, polyvinyl chloto quaternate than theresidue Z. In this case, the quaterride, polyamide and polyurethanefibres, and also fibres nation may be carried out in a manner such thatthe made from polyesters of aromatic dicarboxylic acids, for reaction isdiscontinued after quaternation of the residue example, polyethyleneterephthalate fibres; but they are 2. Alternatively, the quaternatingconditions can be inspecially useful for dyeing and printingpolyacrylonitrile tensified, for example, by the addition of an excessof fibres or polyvinyidene cyanide fibres (Darvan). By polythequaternating agent or by raising the temperature, in acrylonitrilefibres is meant primarily polymers containa manner such that at leastone of the residues D and ing more than for example, 80 to of acryloni-D is quaternated in addition to the residue Z. 75 trile; they may alsocontain 5 to 20% of vinyl acetate,

vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid,acrylic acid esters, methacrylic acid, methacrylic acid esters and thelike. These products are sold, for example, under the following tradenames: Acrilan 1656 (The Chemstrand Corporation, Decatur, Ala., U.S.A.),Acrilan 41 (The Chemstrand Corporation), Creslan (American CyanamidCompany), Orlon 44 (Du Pont), Crylor HH (Soc. Rhodiacta SA, France),Leacryl N (Applicazioni Chimice Societa per Azioni, Italy), Dynel (UnionCarbide Chemical Corporation), Exlan (Japanese Exlan Industry Co.,Japan), Vonnel (Mitsubishi, Japan), Verel" (Tennessee Eastman, U.S.A.),Zefran (Dow Chemical, U.S.A.), Wolcrylon (Filmfabrik Agfa, Wolfen),Ssaniw (U.S.S.R.) and also Orlon 42, Dralon, Courtelle and so forth.

The new dyestuffs produce on these fibres, which may also be dyed inadmixture with one another, intense and level dyeings possessing goodfastness to light and good general properties of fastness, especiallygood fastness to Washing, perspiration, sublimation, crease-resistfinishing, decatizing, hot-pressing, rubbing, carbonizing, water, seawater, dry cleaning, cross-dyeing and solvents.

The present invention therefore also includes a process for dyeingman-made fibres, for example, fibres made from polyurethanes, cellulosetriacetate, cellulose acetate (so-called 2 /2-acetate), fibres made fromlinear aromatic polyesters, for example, those made from terephthalicacid and ethylene glycol or 1,4-dimethylol-cyclohexane and copolymersderived from terephthalic acid isophthalic acid and ethylene glycol,fibres based on polyepoxides, polyamides, for example, nylon 6, nylon6.6 or nylon 12 or polyolefine fibres, for example, modifiedpolypropylene, but especially acrylic fibres made from polyacrylonitrileand copolymers of acrylonitrile and other vinyl compounds, for example,acrylic acid, acrylic esters, acrylamides, methacrylic acid, methacrylicesters, methacrylic amides, vinyl pyridine, vinyl chloride or vinylidenechloride, copolymers of dicyanoethylene and vinyl acetate, and alsoacrylonitrile block polymers, wherein disazo compounds are used in whichtwo monoazo dyestuff molecules of the general formula in which Drepresents the residue of a monocyclic or bicyclic diazo component, Arepresents an arylene residue and R and R" each represents an alkylresidue, are linked toegther via their coupling components through abifunctional bridging group Z which has no dyestutf characteristics andwhich contains at least one quaternated nitrogen atom.

The new dyestuffs of the invention display, inter alia, good stabilityin a wide pH range and good afiinity, for example, in aqueous solutionshaving different pH values. Furthermore, the new dyestuffs generallyshow good reservation on wool and other natural or synthetic polyamidefibres.

Generally, the quaternated water-soluble dyestufis display littlesensitivity to electrolytes, and some of them have markedly goodsolubility in water or organic solvents. Dyeing with the quaternatedwater-soluble dyestuffs is generally carried out in an aqueous neutralor acid medium at the boil under atmospheric pressure or in a closedvessel under superatmospheric pressure at higher temperatures. Thecommercially available levelling agents have no adverse effect, but theyare not necessary. The dyestuffs mentioned are also very suitable forthreecolour dyeing. By virtue of their stability towards hydrolysis,they may be used advantageously for high-temperature dyeing and fordyeing in the presence of wool. They may also be applied to the fibrousmaterials by printing processes. In this method of application there isused, for example, a printing paste which contains the dyestuff and theadjuvants commonly used in printing, for example, wetting agents andthickeners.

The dyestuffs of the invention are also suitable for colouringpolymerization products of acrylonitrile and other plastics by additionto the composition or a solution thereof, prior to the shapingoperation, the shades obtained being fast to light and washing.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

PREPARATION OF THE COUPLING COMPONENTS Procedure I 31.9 parts ofN-ethyl-N,2-hydroxyethylanilinc-paratoluene-sulphonic acid ethyl esterand 19.2 parts of N- ethyl N,2 (N,N dimethylamino) ethylaniline arestirred for 3 hours at to C. and the honeycoloured liquid which forms istreated with 200 parts of ethyl acetate. The condensation productprecipitates in the form of white needles. After cooling, the product isisolated by filtration and washed with a small amount of ethylacetate.The coupling component of the formula CH3 so obtained melts at 123 C.

Further coupling components of this kind may be obtained in an analogousmanner by reacting the toluenesulphonic acid esters listed in column IIof the following table with the tertiary amines shown in column III.

Procedure 11 5, ,5',7-Diepoxytripropylamine (prepared in accordance withFrench patent specification No. 1,137,175) are heated with ethyanilinein chlorobenzene to yield 5,5- dihydroxy 'y,'y'di(N-phenyl-N-ethyl)-aminotripropylamine. The product is then acetylatedwith an excess of acetic anhydride and the reaction mixture evaporatedin vacuo to yield B,,B-diacetoxy-'y,' '-di(N-phenyl-N-ethyD-aminotripropylamine of the formula Procedure III Procedure IV 23.3 partsof N,2-(N'-phenyl-N'-ethyl)-aminoethylpiperidine, 10.1 parts of1,3-dibromopropane and 25 parts of dimethylformamide are stirred for 3hours at 140 to 145 C. until no turbidity forms on dilution with water.The solvent is evaporated in vacuo and the residue is dissolved in 100parts of water. The solution of the compound of the formula is obtained.A thin-layer chromatogram shows that the solution is free fromlay-products.

An analogous compound in which the two positively charged nitrogen atomsare linked by a bridge consisting of four methylene groups is obtainedwhen the 1,3-dibromopropane is replaced by 1,4-dibromobutane.

The following bifunctional coupling components may also be obtained inan analogous manner:

CH5 H2C\ O H4-l I--(CH )a-III-CzH4 H3 CH3 H N CHa I an.

Procedure V 256 parts of the toluenesulphonic acid ester of N-alkyl-N,2-hydroxyethylaniline, 290 parts of ethanol and parts of 35% aqueousmethylamine solution are vigorously heated for 1 hour under reflux. Thesolvent is evaporated, the residue is taken up in 800 parts of water,parts by volume of 30% sodium hydroxide solution are added, the mixtureextracted with chloroform, the chloroform extract is dried with calcinedsodium sulphate, the solvent is evaporated and the residue is distilled.The compound of the formula C2 4N z 14 is obtained at 15 6 to 158 C.under a pressure of 0.04 mm.

CgHs

Procedure VI 64 parts of the toluenesulphonic acid ester of N-ethyl-N,2-hydroxyethylaniline, 17.2 parts ofN,N,N',N'-tetramethylhexamethylenediamine and parts of dimethylformamideare heated to 70 C., whereupon the exothermic reaction raises thetemperature of the reaction mixture to 120 C. After the reactionsubsides, the batch is heated again to the boil and then allowed tocool. The crystal slurry so formed is diluted with 400 parts of ethylacetate, suction filtered, and the filter residue is washed with ethylacetate. 79 parts of the compound of the formula +2 0 a 211s e k I a Ha2 Q C gHr-N- (CH2) 6-NC24 C H; are obtained.

Procedure VII 236 parts of3-diethylaminophenol-2'-dimethylaminoethylether, 108 parts of1,4-dibromobutane and 200 parts of dimethylformamide are stirred for 12hours at 120 to C., the mixture is allowed to cool, 400 parts of waterare added, and the batch is then stirred until the coupling componentcrystallizes. The product is isolated by suction filtration, washed with400 parts of a 10% sodium bromide solution, dried, and the compound ofthe formula 10.2 parts of the coupling component prepared in accordancewith Procedure I by quaternation of N-ethyl-N,5-(N',N'-dimethylamino)ethylaniline are dissolved in 500 parts ofwater and 10 parts of glacial acetic acid. A diazo solution preparedfrom 69 parts of a 10% aqueous paste of 2-chloro-4-nitroaniline bydiazotization with sodium nitrite and hydrochloric acid is run into thesolution so obtained, the coupling mixture is rendered neutral to Congored by the addition of sodium acetate crystals, and the batch is stirredat to C. until the diazo compound is no longer detectable. The dyestufi,which is sparingly soluble in cold water, is isolated by filtration anddried. When applied in an aqueous bath it dyes polyacrylonitrile fibresa red shade possessing very good fastness to light. The dyestuffcorresponds to the formula C2115 H5 C3 Dyestuffs which yield the shadeslisted in column III of the following table may be obtained by replacingthe (I) 01 N O- ll l 2-ch1oro-4-nitroaniline with the diazo componentslisted in column II.

EXAMPLE 2 5.36 parts of the monoazo dyestuff of the formula Dyeingprocedure 1 part of the dyestuif so obtained of the formula is dissolvedin 5,000 parts of water in the presence of 2 parts of acetic acid. 100parts of dried polyacrylonitrile staple fibre yarn are entered into thisdyebath at C., the temperature is raised to C. within half 40 an hourand dyeing is carried out for one hour at the boil.

3.3 parts of 2-cyan0-4-nitroaniline are diazotized at 20 C. in 20 partsby volume of N nitrosylsulphuric acid (obtained by coupling diazotized4-amino-3-chlorophenylmethylsulphone WithN-ethyl-N,2-hydroxyethylanilineand then discharged on to 200 parts ofice. A solution of 4.97 parts of[3,[3'-diacet0Xy-'y,'y'-di-(N-phenyl-N-ethpara-toluene-sulphonic acidester) and 3.5 parts of the 60 yl)-aminotripropylamine in 50 parts byvolume of dimonoazo dyestuff of the formula HCN z s OzHr methylformamideis added dropwise to this solution at a temperature not exceeding 10 C.,the batch is stirred for 3 hours, neutralized with 30% NaOH and stirredovernight. The dyestuif is isolated by filtration and dried in 5 vacuo.The dystufi so obtained corresponds to the formula The dried dyestuff ofthe preceding formula is then suspended in 50 parts of chloro'benzene,the suspension is heated to 85 C. and a small excess of dimethylsulphate is slowly added. The batch is kept at that temperature for 3hours, allowed to cool, filtered, and the residue is taken up in water.Finally, the dyestutf of the formula is salted out, isolated byfiltration and dried. It dyes polyacrylonitrile a violet shade.Dyestuifs which dye acrylic fibres the shades listed in column III ofthe following table may be obtained by 5 proceeding in the above mannerand coupling the coupling components listed in column II with the diazocomponents given in column I.

I II III 1 o N NH /C2 s Red.

Cl CzHa-N-(CHzh 2 Same as above C2Hs Red.

Cz 4N( 2)2 3 Same as above .L Ruby.

ens-Q-rxm 4 C N NE /CzH5 +2 Red.

2 2 N CH);

J 5 l CzH4N-CH2 5 Blue.-

'N F +2 I l H OzN NH2 5 N CH3 gnaw- 0H2):-

6 Cl Yellowish brown.

l /C2H5 +2 Os r l 2 4-N( H2)a Cl 7 Same as above Ruby.

O2N Q-NH2 8 Same as above Do.

/C2H5 H502\ O'\ )Q CQH4-N-CQH| 9 .-do I 0 Do.

a HaO\ )Q C:H4NC2H4 10 01 0 CH Brown.

l C2115 H30 OzN- -NH2 -N CH; N

Ha a 23 24 TABLEContinued I II III 11 OCHa Red.

02N-NH: 02m H30 Q N C1 CzHr-N-CzI-h CH3 CH3 12 N CH H;C\ Reddish blue.

I I OzN NH: l

S C2H4NC2H4 l CH3 13 Same as above Blue.

N (EH: l zH4N- C2H 14 CHzCHzCN NC-CHzHzC Scarlet.

II II N CH; N N C-NH2 I \S CzH N C2114 15 CHzCHzCN NC-CHz-HzC Yellow.

CHaOzS -NH2 01 C2H III C2H EXAMPLE 4 EXAMPLE 5 in 300 parts of glacialacetic acid. The batch is neutralized by the addition of 200 parts ofsoium acetate crystals at C., diluted with 200 parts of ice water andthen stirred for 6 hours at 0 to C. Precipitation of the dyestutf iscompleted by the addition of 40 parts of sodium bromide. The dyestuff isisolated by suction filtration and dried.

The dyestuff so obtained corresponds to the formula r CH;CH NCH CH It isreadily soluble in hot water and dyes acrylic fibres a violet shadepossessing good properties of fastness.

1 mol of N-bis-p-hydroxyethyl-3-nitroaniline, together with 2.2 mols ofacetic anhydride, are heated for 3 hours at 130 C., the acetic acid isthen removed in vacuo and the residue is distilled in a high vacuum.N-bis-fi-acetoxyethyl-3-nitroaniline is obtained.

2 mols of N-bis-B-acetoxyethyl-3-nitroaniline are hydrogenated in 2litres of absolute ethanol in the presence of Pd/ charcoal; the solventis then removed in vacuo and the residue is distilled in a high vacuum.N-bis-fi-acetoxyethyl-3-aminoaniline is obtained.

Preparation of the bifunctional coupling component 5.1 parts ofpyridine-2,6-dicarboxylic acid chloride in 50 parts by volume ofchlorobenzene are added slowly at room temperature to 14 parts ofN-bis-B-acetoxyethyl- Z-aminoaniline dissolved in 50 parts by volume ofanhydrous chlorobenzene. The batch is heated to to C. and stirredovernight at that temperature. After cooling, the chlorobenzene isdecanted and the residue is triturated with ether. The product is thenisolated by filtration and dried.

8.22 parts of 3-chloro-4-aminophenylmethylsulphone are diazotized in Nni-trosylsulphuric acid. The solution so obtained is added dropwise at atemperature not exceeding 10 C. to a solution of 13.82 parts of thebifunctional coupling component dissolved in 200 parts by volume ofdimethylformamide. The batch is stirred overnight at 0 to 10 C. and thedyestuff is precipitated by the addition of ice and water. The dyestufiis isolated by filtration and dried in vacuo, and then 3 parts of thedyestuif so obtained are heated in 75 parts by volume of nitrobenzene at75 C. and stirred until the dyestutf is completely dissolved. 3 parts byvolume of dimethyl sulphate are then added, the batch is heated to 90 C.and then stirred for 25 5 hours at that temperature. The nitrobenzene isremoved by steam and the dyestutf is salted out of the aqueous solutionthat remains with sodium chloride. The dyestuff is isolated byfiltration and dried. It corresponds to the formula and dyes modifiedacrylic fibres, nylon-6,6 fibres, wool fabrics and silk a red shade.

Example 6 30 parts of N-ethylaniline, 17.1 parts of B,'y,B',''-diepoxytripropylamine, 30 parts by volume of chlorobenzene and 10drops of triethylamine are stirred for 30 hours at 140 to 150 C. Thesolvent is then removed in vacuo and the residue is distilled in a highvacum. B,fi-Dihydroxy-' '-di-(N-phenyl-N-ethylamino) tripropylamine isobtained in the form of a viscous oil.

30 parts of B,B'-dihydroxy-y,'-di-(N-phenyl-N-ethylamino)-tripropylamine together with 100 parts byvolume of acetic anhydride are heated for 3 hours under reflux. Thesolvent is then removed in vacuo and the residue is distilled in a highvacuum. p,,8'-Diacetoxy-'y,'y-

di-(N-phenyl-N-ethylamino)-tripropylamine which cou-.

ples bifunctionally is obtained in the form of an oil.

3.88 parts of 2-amino-6-ethoxybenzthiazole are diazotized at to 5 C. in20 parts by volume of N nitrosylsulphuric acid in the presence ofglacial acetic acid/propionic acid, and the solution is then addeddropwise at a temperature not exceeding C. to a solution of 4.97 partsof the bifunctional coupling component in 200 ml. of acetone. The batchis then stirred overnight at 0 to 5 C., neutralized with 30% sodiumhydroxide solution and the dyestuif is precipitated by the addition ofwater. It is isolated by filtration and dried in vacuo. 3 parts of thedyestulf so obtained are heated to 75 C. in 75 parts by volume ofnitrobenzene and the batch is stirred until the dyestufr" has completelydissolved. 6 parts by volume of dimethyl sulphate are added, the batchis heated to 90 C. and stirred for 5 hours at that temperature. Thenitrobenzene is then removed with steam, the aqueous soltuion whichremains is filtered, and the dyestufi in the filtrate is salted out withsodium chloride. After filtration and drying, a dyestuff of the formulais obtained which dyes polyacrylonitrile a blue shade possessing goodproperties of fastness.

26 We claim: 1. Disazo compound which corresponds to the formula l iRgRQX4 in which x x x and x each represents zero or 1 and x +x +x +x =2; R RR' R' R' and R'.; each represents alkyl of up to 4 carbon atoms,cyanoalkyl of up to 3 carbon atoms, alkoyalkyl of up to 5 carbon atoms,hydroxyethyl, nitroethyl, chloroethyl, [3,fi,B-trifiuoromethyl,alkanoylaminoalkyl of up to 4 carbon atoms, alkanoyloxyalkyl of up to 5carbon atoms, alkylsulfonylalkyl of up to 4 carbon atoms,B-(p-chlorobenzenesulfonyl) ethyl, 8 methylcarbamyloxyethyl, [3phenylcarbamyloxyethyl, alkyloxycarbonyloxyalkyl of up to 6 carbonatoms, 'y-acetamidopropyl, fl-(para-nitrophenoxy)- ethyl, B(para-hydroxyphenoxy) ethyl, ,8-(;3'-acetylethoxycarbonyl) ethyl,fi-[B'-(cyano)-ethoxycarbonyl]- ethyl, ,8 [p'(hydroxy)-ethoxycarbonyl]-ethyl, 5-H?- (methoxy) ethoxycarbonyl1-ethyl,[i-[B-(acetoxy)-eth oxycarbonylJ-ethyl, fi-carboxyethyi, 3-aminopropyl,fldiethylamino-ethyl, ,B-cyanoacetoxyethyl, fatty acid acyloxyalkylcontaining up to 5 carbon atoms, or C -C phenylalkyl, and when said R isbound to A forms a tetrahydro-quinoline ring and when said R is bound toA forms a tetrahydro-quinoline ring; R and R each is alkylene of up to 3carbon atoms or a group of the formula wherein Ac represents alkanoyl ofup to 3 carbon atoms, benzoyl, stearoyl, methanesulphonyl,ethanesulphonyl, para-toluenesulphonyl, phenoxycarbonyl,methoxycarbonyl, phenylanrinocarbonyl, methylaminocarbonyl oraminocarbonyl; A and A each is a phenylene group of the formula whereinC and d each represents hydrogen, C -alkyl, C -alkoxy, acetylamino,phenoxycarbonylamino, methoxycarbonylamino or aminocarbouylamino; theazo group and the dialkylamino group in said formula are attached inpara-position to each other; D and D each represents the residue of adiazo component of the benzene 0r naphthalene series and Z is selectedfrom the group consisting of (l) a residue of the formula NH-CO-Z'-CONHwherein Z is a heterocyclic containing up to 6 carbon atoms andcontaining hetero atoms selected from the group consisting of nitrogenand oxygen. (2) a group selected from the formulae r- Y- Y --I I C O-alkylene-N and I'\T+ R5 R6 R5 R in which Y- represents an anion and Rand R together form an alkylene chain that may be interrupted by ahetero atom selected from the group 27 consisting of nitrogen, oxygenand sulfur and contains up to carbon atoms; (3) when R; and R form apart of a tetrahydroquinoline structure, or when X or X; is 1, or when Rand R are fi-acetoxy-propylene, Z is a group of the formula R4 R'swherein R and R' are C C -alkyl; or a group of the formula Y Y" -I I-C1Ca-alkylene-I \I R4 a R4 Ro 2. Disazo compound which corresponds tothe formula in which x x x and x each represents zero or 1 and 1+ 2+ 3+4= 1, 2, 'l 'z, 'a, '4 each p sents alkyl of up to 4 carbon atoms,cyanoalkyl of up to 3 carbon atoms, alkoxyalkyl of up to 5 carbon atoms,hydroxyethyl, fatty acid acyloxyalkyl containing up to 5 carbon atoms,or C C -phenylalkyl, and when said R is bound to A forms atetrahydro-quinoline ring and when said R is bound to A forms atetrahydroquinoline ring; R and R each is alkylene of up to 3 carbonatoms or alkylene substituted with alkylcarbonyloxy containing up to 3carbon atoms; A and A each is phenylene or phenylene substituted withmethyl, methoxy, chlorine or acetylamino; the azo group and thedialkylamino group in said formula are attached in para-position to eachother; D and D each represents the residue of a monocyclic or bicyclicdiazo component of the benzene or naphthalene series and Z is selectedfrom the group consisting of (1) a residue of the formula wherein Z' isa heterocyclic containing up to 6 carbon atoms, and containing heteroatoms selected from the group consisting of nitrogen and oxygen; (2) agroup selected from the formulae Y Y N O C alkylene;N and R5 Ru R5 R6wherein R' and R' are C C -alkyl, or a group of the formula Y- Y 5+ 3+NC -C a1kylene-N- R's Ra 's R'o 3. Disazo compound as claimed in claim2, in which the bridging group Z contains at least one group of theformula in which Y represents an anion and R and R together form analkylene chain that may be interrupted by a hetero atom, or part of aring.

4. Disazo compound as claimed in claim 2, in which x =l and x ==1.

5. Disazo compound as claimed in claim 2, in which the residues R and Reach is an ethylene bridge.

6. Disazo compound as claimed in claim 2, which corresponds to theformula 7. A dyestuif according to claim 2 of the formula 8. A dyestulfaccording to claim 2 of the formula 29 30 9. A dyestuif according toclaim 2 of the formula CF H3 +3 CZHE N=NN 011170) CIHEO s CHr-CHFOH2 N+-v ICCH3 H3 C1 3,346,553 /1967 Kuhne et a1. 260-163 References Cited3,454,552 7/1969 Yamaya et a1. 260-155 UNITED STATES PATENTS 3,480,61211/1969 Cain 260158 X 15 1,887,996 11/1932 Conzettl 260-156 L 2,099,52511/1937 Krzikalla m1 260-156 F OYD HIGEL Primary Exammer 2,219,28010/1940 Graeneckereta1. 260-156 2,2 2 1 4 i y eta-1 260-156 84, 41 R, 41A, 41 B, 41 c, 41 D, 51, 71; 117138.8 R, 2,945,849 7/1960 Kruckenberg et2150-186X 138.8 D, 138.8 F, 138.8 PV, 144; 260152, 156, 157, 3,117,9601/1964 v 260-456 158, 160, 163, 174, 178, 187, 205, 247.5 R, 268 TR,3,148,181 9/ 19.64 9 et ah X 268 PC, 288 R, 288 A, 293 D, 294 A, 456 A,463, 465 E, 3,234,208 2/1966 Llechtl 260-452 X 472, 501.15, 553 A, 556A, 558 A, 567.6 M, 567.6 P, 3,252,964 5/1966 Fuchs et a1 260152 567.6 B,570.5 P 3,271,383 1/1966 Yamaya et a1 260-158 CASE 6183/E UNITED STATESPATENT OFFIGE CERTIFICATE OF CORRECTION Patent No. 3,635,9uo DatedJanuary 18, 1972 j Inventor(s) GERT 'HEGAR ET AL It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

F v a 5 Column 26, line 18, change "alkoyalkyl" to read alkoxyalkylColumn 27, line 13, on the left-hand side of the formula change ",Y" toread Y Column 28, line 25, in the middle of the formula change "0 toread C Signed and eealed this 15th day of August 1972.

(SEAL) Attest:

EDWARD M .FLEI CHER JR ROBERT GOT'ISCHALK Attesting Officer Commissionerof Patents

